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The transition‐metal‐catalyzed cyclization of bissilylethynylated N,N’‐dihydrotetraazapentacene (TIPS‐TAP‐H2) into bissilylated cyclopenta[fg,qr]pentacenes is reported. Depending on the catalyst either none, one or two silyl groups migrate and change their positions in the formed five‐membered rings. The optoelectronic properties are quite similar, whereas the packing motifs differ dramatically. Control...
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